Process for purifying trifluoro-chloroethylene



April 22, 1958 J. s. REARlcK ETAL PROCESS FOR PURIFYING TRIFLUOROCHLOROETHYLENE original Filed sept. 15, 1952 INVENTORS` JOHN s. REAmCK BY ROBERT P. SCHAAF ($1.9 .1 Y JURA/5y;

United States Patent() PROCESS FOR PURIFYING TRIFLUORO- CHLOROETHYLENE John S. Rearick, Dover, N. J., and Robert P. Schaaf, East Orange, N. J., assignors, by mesne assignments, to Minnesota Mining and Manufacturing Company, St. Paul, Minn., a corporation of Delaware Original application `September 13, 1952, Serial No. 309,434, now Patent No. 2,742,454, dated April 17, 1956. Divided and this application Detober 31, 1955, Serial No. 546,922

s Claims. (ci. '26o- 653) This invention relates to a process for the manufacture of normally solid perhalogenated polymers. In one of its aspects this invention relates to a continuous method for the production of solid polymers of trifluorochloroethylene. In still another aspect this invention relates to the purification of monomer for the production of solid perhalogenated polymers.

Prior to the present invention trifluorochloroethylene has been polymerized and copolymerized in a batch type of operation. In the batch type of operation the monomer is introduced into a reaction bomb together with a suitable promoter and the temperature of the bomb is maintained at about 16 C. or -l7 C. for a period of about seven days. In this time the monomer is polymerized to form a porous plug of solid polymer in the reaction bomb with approximately 30 to 50 percent yield of polymer based on monomer charged. The unreacted monomer is occluded in the interstices `of the porous plug and is removed therefrom by heating the reaction bomb under subatmospheric pressure to evaporate unreacted monomer. The dried porous plug of polymer of tn'uorochloroethylene is removed from the reaction vessel and broken into chips or granules for shipment in handling.

The bomb reactor is about 6 inches in diameter and is placed in a liquid cooling bath. Larger diameter bombs cannot be used because of the poor heattransfer of the monomer and solid polymer.

Thewbomb type of operation for the production of solid polymers of tritiuorochloroethylene and other perhalogenated oleins has its inherent disadvantages. The apparatus and equipment is cumbersome with relatively low capacity. The accompanying labor costs are high. However, the yield of product based on monomer is high and the purity and physical characteristics of the resulting polymer are exceptionally good providing the monomer is adequately purified.

To overcome the low capacity and high labor costs for` the polymerization of triuorochloroethylene in the bomb type reactors, continuous slurry type methods have been proposed. In such previously proposed continuous process the monomer is produced by dechlorination of triuorotrichloroethane by zinc in the presence of methanol. The crude monomer from the dechlorination still is then passed through a series of distillation columns to remove the high1 boiling contaminants of the crude monomer. Puried monomer is recovered from the overhead from the last distillation column. The distilled monomer is then contacted with an appropriate absorption medium to remove the last traces of methanol and any water that may be present. According to such continuous process, the monomer is then polymerized in an autoclave type of reaction vessel and la slurry of monomer and solid polymer is withdrawn from the autoclave and subjected solid polymer.

ICC

Certain disadvantages have been found in the above proposed continuous process for the production of solid polytriluorochloroethylene. In employing distillation to purify the monomer it was found substantially impossible to remove the last traces of the methanol because it formed an azeotrope with monomer. The methanol contamination of the monomer affected the chemical and physical characteristics of the ultim-ate polymer and results in a polymer of inferior characteristics. The presence of said contaminant also adversely aiected the rate of polymerization and the yield of polymer therefrom. Handling of the polymerization mixture during poly merization presented a problem because of the high viscosity of the monomer-polymer slurry. The monomerpolymer slurry is very difiicult to circulate in the polymerization zone and during subsequent recovery steps. The high viscosity of the monomer slurrywas due primarily to the high absorption of monomer in the solid polymer. The recovery of solid polymer from monomer by filtration is also diticult because of the high absorp tion of monomer in solid polymer. It is, therefore, the purpose of this invention to overcome the above difliculties of both the bomb type of operation and previously proposed continuous type of operation as described above.

The object of this invention is to provide a continuous process for the polymerization of perhalogenated oleins to produce normally solid homopolymers and copolymers.

Another object of this invention is to provide a method for purifying monomer.

Another object of this invention is to provide a method for recovering dried solid polymer from a monomer slurry thereof.

There is still a further object of this invention to provide an integrated continuous process for the purication of monomer, polymerization of the monomer to produce a solid polymer andthe recovery of monomer from solid polymer product.

A further object of this invention is to provide a process for large capacity production of normally solid polymers of tritluorochloroethylene, such as the thermoplastic polymer` having an N. S. T. between about 240 C. and about 350 C.

Yet another object of this invention is to provide a continuous process for the polymerization of trifluorochloroethylene whereby the costs of production are sub stantially decreased. t

Various other objects and advantages of the present invention will become apparent to those skilled in the art from the accompanying description and disclosure.

This invention applies generally to the polymerization of perhalogenated olens to produce both solid homopolymers and copolymers. A perhalo olen is defined as an olefin consisting of carbon and halogen with any degree of unsaturation; preferably according to this invention, the perhalo olefin contains fluorine, or chlorine, or both as the halogens. According to this invention a saturated luorochloro carbon is dechlorinated under suitable conditions of dechlorination in the presence of a metallic dehalogenating agent to produce a peruorohalo monoolelin as a monomer for subsequent polymerization. The dechlorination is carried out in the presence of a suitable solvent, such as methanol or ethanol. The crude monomer effluent containing both higher boiling and lower boiling contaminants is removed from the dechlorination reactor4 and purified. The major contaminants of the crude monomer are the solvent, such as methanol, and other perhalo olens or perhalo parains. Accordingly, the crude monomer is water washed to effectively remove substantially all of the methanol or water soluble solvent. After water washing, the water washed monomer isthcn dried under conditions such thaty @sensor 3 the monomer contains less than about 100 p. p. n1., preferably less than 10 p. p. m. of water, and distilled to remove low boiling impurities. After removal of the low boiling impurities the monomer bottoms from the tirst distillation is subjected to a second distillation to remove the high boiling impurities. Best results are obtained by distillation at pressures above 100 pounds per square inch gage. Thereafter, the purified monomer is polymerized in a horizontal ilow elongated reactor to form a slurry of solid polymer and monomer having a concentration not more than about 12 weight percent polymer in monomer. The polymerization is effected generally at a temperature between about F. and about 60 F. or 70 F. under liquid phase conditions for a period of time between about 2 and about 40 hours. The slurry of polymer and monomer is then dried at an elevated temperature above about 150 F. to recover the polymer. The solid polymer is recovered as a product of the process. At least a portion of the recovered monomer is recycled to purification step to prevent the build up of impurities in the recycle.

The present invention is applicable to the homopolymerization of tritluorochloroethylene and to the copoly merization of triiluorochloroethylene with other halogenated fiuorine containing olefins having no more hydrogen atoms than the number of carbon atoms. Such copolymerizations include the copolymerization of trilluorochloroethylene with tetrafluoroethylene, perfluoropropene, peruorobutadiene, vinylidene fluoride, triuoroethylene, monouorochloroethylene, monotluorotrichloroethylene and difluorodichloropropene. In the copolymerization it is usually preferred to employ between about 5 and 95 weight percent of comonomer with triiluorochloroethylene. The conditions of polymerization of the copolymers of triuorochloroethylene are substantially the same as for the homopolymerization of triuorochloroethylene. The following discussion of the general application of the present invention to the polymerization oi trifluorochloroethylene applies substantially to all copolymerization systems with triuorochloroethylene.

For a better understanding of the present invention reference will be made to the accompanying drawing which diagrammatically illustrates a suitable arrangement of apparatus in elevation which is used for the production of normally solid plastic homopolymers and copolymers of trifluorochloroethylene. The principal pieces of apparatus for effecting the process depicted in the drawing comprise a dehalogenator 12, a water wash tower 24, distillation columns 38 and 43, polymerization reactor 58, spray dryer 71, cyclone separator 73 and concentrator 105. The process will be described in the drawing for the polymerization of triuorochloroethylene to produce the homopolymer thereof. It will be understood that the quantities and other operating conditions referred to are for purposes of illustration and may be varied without departing from the scope of the invention.

According to the drawing and the process illustrated, triuorotrichloroethane of the l,2,2, chloro structure, which may be obtained commercially on the open market as Freon 1l, is passed through conduit 11 to dehalogenator 12. A metallic dechlorinating agent, such as zinc dust, is introduced into dehalogenator 12 through means not shown. Although zinc is preferred various metal dechlorinating agents may be used, such as tin, manganese, magnesium and iron without departing from the scope of this invention. A suitable solvent or diluent is introduced into dehalogenator 12 through conduit 11. The preferred solvent is methanol. However, ethanol has also shown good results and there are various other conventional solvents for use in such a process. The miX- ture of trifluorotrichloroethane, solvent and zinc is vigorously agitated by conventional means, such as a stirrer, as shown. Dehalogenator 12 is maintainedv at a pressure of about 150 pounds per square inch gage and` at a temperature of about 210 F. The temperature conditions are produced initially by steam in the jacket of the reactor. Once the reaction has been initiated it is self sustaining and cooling water is used in the jacket to control the reaction. Under these conditions Freon 113 is dechlorinated to tritluorochloroethylene which is passed overhead through dephlegmator 13 which removes a portion of entrained and vaporized methanol Freon 113 and other contaminants. The crude monomer is passed through conduit 14, condenser 16 to accumulator 17. The temperature of the material leaving dephlegmator 13 is approximately F. and is reduced to a temperature of approximately 100 F. by conventional cooler 16. The pressure in accumulator 17 is approximately 150 pounds per square inch gage. A portion of condensate in accumulator 17 is recycled to dephlegmator 13 as reflux through conduit 18. Zinc chloride and the bottoms from the reaction in dehalogenator 12 may be removed therefrom through conduit 21. Conduit 19 is for the purpose of venting accumulator 17 to prevent the build up of pressure in the system.

Approximately 380 pounds pei` hour of monomer is passed from accumulator 17 through conduit 22 by means of pump 23 to the upper portion of water wash tower 24. Deaerated water is introduced into the bottom of tower 24 through conduit 25 at a rate of about 350 pounds per hour and countercurrently contacts downllowing liquid monomer. Washed liquid monomer substantially free from methanol is passed through conduit 26 to dryers 34 and 36 containing calcium sulfate. Dryers 34 and 36 may contain any conventional type of drying material, such as disclosed in Patent No. 2,600,804. The water wash is removed from the upper portion of tower 24 through conduit 2'7 and is passed to accumulator or separator 28. About 350 pounds per hour of water is removed from separator 28 thro-ugh conduit 29. This water contains dissolved methanol. Any entrained or dissolved monomer is removed from the upper portion of accumulator 28 as vapor through .conduit 31 and is passed to dryer 32 containing calcium sulfate. The dried monomer vapor is then recycled through conduit 33. The water washed and dried liquid monomer from the bottom of tower 24 is passed through conduit 37 to the intermediate portion of a distillation column 38. This monomer stream contains on an hourly basis approximately 691 pounds of monomer, 2.46 pounds of trilluoroethylene, 2.96 of diuorovinyl -chloride and 2.58 pounds of trichloromonouoromethane. In distillation `column 38, separation is made between monomer and lower boiling impurities, such as triuoroethylene together with minor amounts of other impurities. Conventional reboiler 39 maintains the bottom temperature of tower 38 at about F. Liquid monomer substantially free from tritiuoroethylene is removed from tower 38 through conduit 41. The vaporous overhead fraction from tower 38 containing monomer, triliuoroethylene and minor amounts of other light impurities is removed therefrom through conduit 42 and is passed through a conventional cooling means 43 to an accumulator 44. The temperature and pressure maintained in accumulator 44 is about 170 pounds per square inch gage and 80 F. Uncondensables may be vented through conduit 48, if necessary. Approximately 706 pounds of the overhead fraction is recycled as reflux from accumulator44 to distillation tower 38 through conduit 46. Approximately 2.46 pounds per hour of triuoroethylene and approximately 2.34 pounds per hour of monomer are recovered from accumulator 44 through conduit 47. The top temperature of distillation tower 38 is maintained at about 94 F.

The liquid monomer stream in conduit 41 is substantially free from triuoroethylene and light impurities but contains difluorovinyl chloride, trichloromonolluoromethane and higher boiling impurities. This stream is passed through conduits 41 and/ or 4S into the intermediate portion of a distillation tower S0. Element 60is a reboiler which maintains a bottom temperature of about 125 F.

in tower 50. A liquid bottoms fraction comprising 'about 4.66 pounds of monomer, about 2.96 pounds of diuorovinyl chloride, about 7.38 pounds of trichloromonoiluoromethane per hour and minor amounts of heavy impurities is removed from tower 50 through conduit 75 for disposal or recovery.

A vaporous overhead fraction is removed from distillation tower 50 through conduit 55 and is passed through a conventional cooler 70 to an accumulator 49. Accumulator 49 is maintained at a pressure of about 160 pounds per square inch gage and at a temperature of about 120 F. A portion of the condensate is recycled through conduit 51 to the upper portion of distillation tower 50. This reux stream yamounts to about 7,966 pounds per hour of monomer. A stream of substantially pure monomer is passed through conduit 52 through a conventional cooler 53 to a feed accumulator 54. About 684 pounds per hour of monomer is passed through conduit 52 at 32 F. to accumulator 54. Accumulator 54 is maintained at a temperature of about 32 F. and a pressure of about 30 pounds per square inch gage. Liquid feed monomer is passed from accumulator 54 through conduit 56 to the lower portion of a horizontal polymerization chamber 58. A promoter, such as trichloroacetyl peroxide, is introduced as a solution of appropriate strength in trichloromonouorometh'ane into feed conduit 56. About 7.6 pounds per hour of such solution is introduced through conduit 57.

`-Polymerization chamber 58 comprises a horizontal cylindrical chamber containing bales 61 dividing the chamber into three sections. The monomer polymer slurry in chamber 58 is maintained in a state of agitation in each of the polymerization sections by conventional stirrers 59. The bottom of b'atiies 61 contains openings so that the monomer polymer mixture may ilow horizontally from the entrance of chamber 58 to the exit thereof. just below the top of baffles 61. A monomer polymer slurry containing less than about 12 percent solid polymer, preferably about 5 to 7 percent polymer, is withdrawn from the other end of horizontal chamber 58 through conduit 62. Chamber 58 is maintained at a pressure of about 30 pounds per square inch gage and a temperature of about 32 F. Under these conditions monomer is Vaporized due to heat evolved in the reaction and is removed from the open space at the top of chamber 58 through a conduit 63 and is passed through conduit 64 to a conventional condenser 66. From condenser 66 liquid monomer is recycled through conduits 67 and 52 to accumulator 54. Any monomer vapor evolved from accumulator 54 is also passed to condenser 66 through conduit 64. The amount of monomer recycled through conduits 63 and 64 is about 2,030 pounds per hour at 32 F. The vaporization of this monomer in accumulator 54 and chamber 58 maintains the temperature of polymerization in chamber 58, and the heat of polymerization is removed by condenser 66. Uncondensed vapors are removed from the top of condenser 66 through conduit 68 and are recycled, as shown.

About 2,680 pounds per hour of liquid monomer and about 171 pounds per hour of solid polymer are passed through conduit 62 and pump 69 into spray dryer 71. The outlet temperature of spray dryer 71. is maintained at about 150 F. Vaporized monomer and suspended iinely divided solid polymer are passed from spray dryer '71 through conduit 72 to cyclone separator 73. In cyclone separator 73 solid polymer is separated from Vaporized monomer. Vaporized monomer is recycled to spray dryer 71 through conduit 74 through heater 77 by means ot blower 76. Dried polymer is passed from cyclone separator 73 alternately through conduits 78 and 79 to lock hoppers 81 and 82, respectively. The lockhoppers are used alternately; when one lock hopper is filled, it is emptied by passing solid polymer through conduit 83 to The liquid level in chamber 58 is maintained screw conveyer 86 to storage hopper 87. Solid polymer product is recovered from storage hopper 87 through conduit 89 at a rate of about 171 pounds per hour. This material is passed through conventional extrusion apparatus for extruding the polymer for preparation for packing and shipping. While hopper 82 is being emptied hopper 81 is being filled and, vice versa, when hopper 81 is being emptied through conduit 84 hopper 82 is being filled.

Prior to emptying the hoppers 81 and 82, Vaporized monomer is passed through conduits 91, 92 and 93 to dryer 96. Dryer 96 contains calcium sulfate or other conventional absorbing material to remove impurities so that the impurities will not corrode compressor 97 which is used to compress the monomer for introduction into conduit 68 for recycling. After emptying, lock hoppers 81 and 82 are repressured with nitrogen through conduit 94. The temperature of vaporous monomer from compressor 97 is about 300 F. Monomer is: divided from conduit 74 and a portion passed through conduit 100 at about 150 F. through cooler 102, where the temperature is reduced to about 100 F., to monomer scrubber and concentrator 103. Vaporized monomer containing er1- trained inely divided polymer is introduced into the bottom of scrubber 103. About 2,680 pounds per hour of monomer is passed through conduit 100 to scrubber 103. Scrubber 103 contains a condensing yor cooling element 105 in the top thereof to condense upwardly llowing monomer, which then ows as liquid to the bottom of scrubber 103. Scrubber 103 is maintained at a pressure of about 35 pounds per square inch gage and about 40 F. Liquid monomer is recycled by means of pump 107 through conduit 106 to the upper portion of scrubber 103 to scrub solids from the vaporous monomer. The liquid in the bottom of scrubber 103 contains finely divided polymer recovered in concentrated lform and is recycled through conduit 104 to conduit 56 for return to polymerization vessel 58. The amount of monomer thus returned is approximately 2,167 pounds per hour through conduit 104. The temperature of this stream is about 32 F. About 320 pounds per hour of the liquid monomer in the bottom of scrubber 103 is passed through .conduit 108 by means of pump 109 to conduit 22 for repurication. V aporized monomer from scrubber 103 is passed to conduit 68. The vaporous monomer in conduit 68 is passed through absorber 98 containing calcium sulfate. This absorber is used to remove contaminants which might corrode subsequent compressor 99. From absorber 98, vaporous monomer is passed through conduit 68 by means of compressor 99 at a rate of about 193 pounds per hour and pounds per square inch gage and at a temperatpre of 240 F. through cooler 101 to accumulator 17. Cboler 1.01 cools the monomer to about 100 F.

The conditions of operation of dehalogenator 12 and polymerization chamber 58, including the types of promoters and solvents, may be carried out in accordance with the teachings of Patent No. 2,600,804. Although different reaction conditions may be employed, such as temperature in chamber 58, if the reaction conditions are changed, the pressure and temperature conditions in the entire system is changed accordingly. Various modifications of the materials used and operating conditions may be employed Without departing from the scope of this invention. However, the method of purification, type of polymerization zone and method of recovery of the product are essential features of the present invention andthe integration of these features into a single unitary and continuous process is part of this invention.

Having described our invention, we claim:

1. A process for the purication of triuorochloroethylene which comprises passing a distillate stream of triiluorochloroethylene containing as impurities trace amounts of methanol, triuoroethylene, diuorovinyl chloride and trichloromonoiluoromethane obtained by the dechlorination of trifluorotrichloroethane to a water scrubbing zone, water Iscrubbing said trilluorochloroethylene stream to remove methanol therefrom, passing a trifluor-ochloroethylene stream from said Water scrubbing zone substantially free from methanol containing the other of said impurities and Water to a drying zone, drying said water washed triiinoroethylene stream with `calcium sulfate to remove Water therefrom, passing a triiiuorochloroethylene stream from said drying zone substantially free from water and containing trifiuoroethylene, diiluorovinylchloride, and trichloromonouoromethane yas impurities to a first distillation zone, removing an overhead fraction from said first distillation zone comprising triuorochloroethylene and triiiuoroethylene, removing a bottoms fraction from Isaid first distillation zone comprising trifluorochloroethylene, diuorovinylchloride and trichloromonoiluoromethane as impurities, passing said bottoms fraction to a second distillation zone, removing a bottoms fraction from said second distillation zone comprising triiiuorochloroethylene, difluorovinylchloride and trichloromonofluoromethane therefrom, and removing an overhead fraction comprising triliuorochloroethylene from said second distillation zone substantially free from said impurities as the product of the process,

2. A process for purifying trifiuorochloroethylene which comprises passing a distillate stream of triliuorochloroethylene containing as impurities trace amounts of methanol, triilnoroethylene, difluorovinylchloride and trichloromonofluoromethane obtained by the dechlorination lof triiiuorotrichloroethane in the presence of methanol and a metal dechlorinating agent to a Water scrubbing' zone, water scrubbing said stream yof trifluorochloroethylene `to remove methanol therefrom, passing :a triflnorocllloroehylene stream from said Water scrubbing zone substantially free from methanol and -containing the other yof said impurities and Water to a drying zone, drying said water Washed trifluorochloroethylene stream `to remove Water therefrom, passing a triuorochloroethylene stream from said drying zone substantially free from water and containing triuoroethylene, difluorovinylchloride, and trichloromonofiuoromethane as impurities to -a iirst distillation zone, removing a high boiling fraction from said first distillation zone comprising trifluorochloroethylene and diuorovinylc'hloride and trichloromonofluoromethane as impurities and substantially free from tn'uoroethylene, passing said high boiling fraction from said iirst distillation zone to a second distillation zone, and removing a low boiling fraction from said second distillation zone comprising triuorochloroethylene and substantially free from said impuritiesas a product of the process.

3. A process for purifying triuorochloroethylene which comprises passing :a distillate stream of trifluorochloroethylene containing as impurities trace amounts of Water soluble alcohol, trifluoroethylene, diuorovinylchloride and trichloromonofluoromethane, water scrubbing said triluorochloroethylene stream to remove said Water soluble alcohol therefrom, passing a triuorochloroethylene stream from said water scrubbing zone substantially free from said water soluble alcohol and containing the other of said impurities and Water to a drying zone, drying said water Washed ltrifluorochloroethylene stream to remove water therefrom, passing la triliuorochloroethylene stream from said drying zone substantially free from water and containing trifluoroethylene, difluorovinylchloride, and trichloromonoiiuoromethane as impurities to a iirst distillation zone, removing a high boiling fraction from said rst 'distillation zone comprising triuorochloroethylene, land difluorovinylchloride and trichloromonouoromethane as impurities and substantially free from trifluoroethylene, passing said high boiling fraction from said first distillation zone to a second distillation zone and removing a low boiling fraction from said second distillation zone comprising triiiuorochloroethylene and substantially free from said impurities as a product of the process.

References Cited in the iile of this patent UNITED STATES PATENTS `2,120,665 Hanson June 14, 1938 2,543,478 Tooke et `al Feb. 27, 1951 2,558,624 Murray June 26, 1951 2,560,838 Ornold July 17, 1951 2,589,212 Ogapetus et al. Mar. 18, 1952 2,606,937 Colfee et al. Aug. l2, 1952 2,614,129 McBee et al. Oct. 14, 1952 

1. A PROCESS FOR THE PURIFICATION OF TRIFLUOROCHOLOROETHYLENE WHICH COMPRISES PASSING STREAM OF TRIFLUOROCHLOROETHYLENE CONTAINING AS IMPURITIES TRACE AMOUNTS OF METHANOL, TRIFLUOROETHYLENE, DIFLUOROVINYL CHLORIDE AND TRICHLOROMONOFLUOROMETHANE OBTAINED BY THE DECHOLORINATION OF TRIFLUOROTRICHLOROETHANE TO A WATER SCRUBBING ZONE, WATER SCRUBBING SAID TRIFLUOROCHOROETHYLENE STREAM TO REMOVE METHANOL CONTAINING THE FLUOROCHLOROETHYLENE STREAM FROM METHANOL CONTAINING THE ZONE SUBSTANTIALLY FREE FROM METHANOL CONTAINING THE OTHER SAID IMPURITIES AND WATER TO A DRYING ZONE, DRYING SAID WATER WASHED TRIFLUOROETHYLENE STREAM WITH CALCIUM SULFATE TO REMOVE WATER THEREFROM, PASSING A TRIFLUOROCHLOROETHYLENE STREAM FROM SAID DRYING ZONE SUBSTANTIALLY FREE FROM WATER AND CONTAINING TRIFLUOROETHYL- 